CN1102134C - An anti-caking agent - Google Patents

An anti-caking agent Download PDF

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Publication number
CN1102134C
CN1102134C CN96198625A CN96198625A CN1102134C CN 1102134 C CN1102134 C CN 1102134C CN 96198625 A CN96198625 A CN 96198625A CN 96198625 A CN96198625 A CN 96198625A CN 1102134 C CN1102134 C CN 1102134C
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salt
caking agent
represent
hard caking
formula
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CN1202878A (en
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T·阿尔纳斯
T·洛格恩
T·凯卡安帕
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Yara Suomi Oy
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Kemira Agro Oy
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2/00—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic
    • B01J2/30—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic using agents to prevent the granules sticking together; Rendering particulate materials free flowing in general, e.g. making them hydrophobic
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
    • C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
    • C05G3/30—Anti-agglomerating additives; Anti-solidifying additives

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Fertilizers (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Medicines Containing Material From Animals Or Micro-Organisms (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Paper (AREA)
  • Control And Other Processes For Unpacking Of Materials (AREA)
  • Sink And Installation For Waste Water (AREA)
  • Fats And Perfumes (AREA)
  • Indole Compounds (AREA)
  • Glanulating (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)

Abstract

The present invention relates to an anti-caking agent for the treatment of granulate products, where the anti-caking agent is a salt having the general formula (Ia): R1-AB-R2-BA-R1, or the general formula (Ib): R1-BA-R2-AB-R1, in which the groups R1 independently represent monovalent hydrophobic organic groups, the group R2 represents divalent hydrophobic organic groups, the groups A represent independently anionic groups and the groups B represent independently cationic groups. The groups A preferably represent carboxylate ion groups and the groups B preferably represent ammonium ion groups. An anti-caking agent of this kind is very suitable for inhibiting the caking tendency of fertilizers.

Description

Anti-hard caking agent
The present invention relates to a kind of method that suppresses the reagent and the described inhibitor of preparation of partical caking tendency.The present invention also relates to the purposes of described inhibitor in preventing the partical caking, also relate to the partical that contains described inhibitor.
Because of its caking tendency, make many inorganic salt (or salt mixture) and the preservation and the difficult treatment that contain the partical (as fertilizer) of described salt.In addition, playing the dirt tendency also is the problem relevant with these products.
Proposed several methods that address these problems already, as used organic Liniment, and may with the powder reagent coupling of pulverizing.
Hot fertilizer particle can with solid wax shape coating reagent mix particles, wax melted and form protective membrane in surface diffusion.But the waxy compound content of wax and wax shape organic compound, as, fatty amine, aliphatic diamine class, fatty acyl amide and lipid acid and salt, or their mixture.
Cold fertilizer particle is mixed with the compound of the different anti-caking effects with raising usually with the oil coating among the latter.Wherein the most frequently used is fatty amine and polyamine class or their derivative.The most normal being used of amine (as the Tallow, beef amine or based on the amine of Tallow, beef hydrate) that contains the hydrocarbon chain of 16-20 carbon.Use the method for lipid acid also to be seen in report for this purpose.
According to the SU510460 introduction, adopt long-chain two amines, handle ammonium saltpetre as distearyl hexamethylene-diamine or two octadecyl sebasin diamines.
Except that lipid acid, other anionic compound (as sulfonate) is also in order to suppress caking and to play dirt.The mixture of the different salt of being made up of sulfonic acid and alkylsulfonate, wherein, the viscosity alkyl derivative is effective especially for having suppressed dirt, describes in patent CA1276071.
According to introducing poly-hydroxyethyl amine R among the EP-113687 (Neederlandse Stikstof Maatschappij) 1-N[(R 2O) N1-H] 2With poly-hydroxyethyl phosphoric acid ester OP[-(R 3O) N2-R 4, R 5, R 6] 3Neutralized reaction product with other batching as a kind of component of coating reagent, wherein, R 1Representative has the alkyl or the alkenyl of 12-20 carbon atom, R 2And R 3Representative has the alkenyl of 2-4 carbon atom, R 4, R 5And R 6One of be hydrogen, the rest is alkyl or have the alkaryl of 4-12 carbon atom with 4-12 carbon atom, and, n 1And n 2It is any number between 0 to 15.
According to patent SE419175 (KenoGard), the coating reagent that adopts granular or particulate stateization is to preventing caking and having prevented that dirt has good result.Liniment is by the inorganic powder of 20%-60% (weight), the cationic amine R-NH2 of 10%-30% (weight) or R-NH-(CH 2) n-NH 2Wherein: R represents aliphatic series, contains the hydrophobic group of 12 carbon atoms and n at least is any number between 1 to 5, or its salt, the alkoxylated fats primary alconol of the fatty amide of the wax of 5%-35% (weight), 0%-20% (weight) and 5%-35% (weight), wherein, alkyl has at least 8 carbon atoms to form.It is reported that hydrocarbon chain amine plant-derived or animal tallow or oil (as butter) is the most suitable.Amine can generate such as muriate, the salt of acetate or lipid acid.
The part of patent EP48226 (KenoGard) has been introduced similar anti-hard caking agent, include the inorganic powder of 20%-60% (weight), the fatty amide that has 12 carbon atoms in the wax of 10%-35% (weight) or the carboxylic acid chain at least, and the carboxylic acid that in alkyl chain, has 6 carbon atoms at least of 20%-60% (weight) and amine R-NH-(CH 2) n-NH 2Mixture.
The method of describing among the patent DDR207701 for preparing anti-hard caking agent is, adopt the aliphatic amide (can be primary, the second month in a season or tertiary amine) of 5%-30% (weight), aromatic series or the aliphatic fatty acid of 30%-90% (weight), and the aromatics monobasic of 5%-40% (weight) or di-carboxylic acid or their derivative, be mixed in mineral or the fatty oil as raw material, the oil-contg of sneaking at that time, is limited in the 10%-90% of mixture weight.Heated mixt can make component reaction and generate acid amides when temperature reaches 500K.Aliphatic amide can be the residuum of dipropylenetriamine or identical preparation process.Other by product or residue amine and lipid acid or carbon, the derivative of fatty acid of nitrogen product than 7: 1 also can be for adopting.
Still there is great difficulty in above mentioned Liniment aspect performance, the adaptability of technology and the commercial viability though so.
The objective of the invention is to make more effective anti-hard caking agent.Simultaneously, reagent will be suitable for partical as much as possible.Make anti-hard caking agent therewith in the field other partical Liniment compatible also very important.The anti-hard caking agent that reaches above-mentioned standard also should be not too expensive.
Above-mentioned target is achieved by a kind of novel anti-hard caking agent, and according to the present invention, novel anti-hard caking agent is a salt, and molecular formula is (Ia):
R 1-AB-R 2-BA-R 1(Ia) or general formula (Ib):
R 1-BA-R 2-AB-R 1(Ib) wherein, R 1Represent monovalence hydrophobic organic radical independently, R 2Represent divalence hydrophobic organic radical, A represents anion-radicals independently, and B represents cation radical independently.Salt of the present invention is novel, with differing widely in the prior art.Therefore described salt is patentability invention.
Find to have the salt of regular layer structure thus, wherein, hydrophobic organic radical and male-female ion alternation make that the effect of anti-hard caking agent is more remarkable.
General formula (Ia) or cation radical B (Ib) can be any cation radicals, and it forms ion pair with anion-radicals, just salt.Cation radical B is preferred from ion.Such radical ion is as the oxygen sulfonium, ammonium, Tan ， Phosphonium, clock, antimony and bismuth.Preferred ammonium in described is when particularly as (Ia) and (Ib) two anion-radicals B of formula all represent ammonium.
General formula (Ia) or anion-radicals A (Ib) anyly can form ion pair with cation radical, just the anionic group of salt.But preferably, above-mentioned anion-radicals A represents the anion-radicals in organic residue replacing acid.Inorganic oxacid, as carbonic acid, sulfuric acid, sulfurous acid, phosphoric acid, Tripyrophosphoric acid, phosphorous acid, one of them or several hydroxyl are replaced by one or several-oxyl or alkyl, are known as organic residue replacing acid.But preferably, at least one particularly whole anion-radicals A is a carboxylic acid ion.Depend on the preparation approach, but the mixture partial reaction that dicarboxylic acid and amine or carboxylic acid and diamines are formed forms acid amides.But importantly, be in unreacted state to small part carboxyl and amino herein.For instance, whether this can observe weight and be judged because of moisture evaporation reduces by the heating product to the temperature that can form acid amides.
Aforementioned (Ia) and (Ib) R of formula 1Can be any hydrophobic group, but preferred long-chain base, the latter can be saturated or unsaturation, replaces or non-replacement, and ring-type or non-annularity, straight or branched, or may contain fragrant chain, and their skeleton can contain inorganic atoms and heteroatoms.
R 1In oil or wax, very easily mix, so The compounds of this invention and oil or wax when together adopting, suit to be used as the part of inhibitor.For the situation of mineral oil or wax, R 1Preferred hydrocarbon chain.When adopting stronger oil of polarity or wax (as natural oil or wax), R 1Preferably containing to increase polar atom or group.R 1Also preferred package contains siloxanes or fluorocarbons, if oil or wax also comprise it.
Aforementioned to R 1Explanation also be applicable to R 2
According to preferred scheme, (Ia) and (Ib) R in the formula 1Be alkyl, preferred alkyl contains at least 7 carbon atoms, more preferably contains 10-22 carbon atom.According to preferred scheme, R 2Be alkylene, the bivalent hydrocarbon radical of 1-22 carbon atom is just arranged, particularly have 2-8 carbon atom person.
According to the present invention, anti-hard caking agent is preferably as the salt of general formula (II): R 1-N (R 3R 4R 5) +-OOC-R 2-COO +-N (R 4R 5R 6)-R 1(II) wherein, R 1, R 2Definition the same, R 3, R 4And R 5Represent hydrogen and the alkyl with 1-2 atom, preferably all R 3, R 4And R 5Represent hydrogen.The also salt of preferred formula (III): R 1-COO- +N (R 3R 4R 5)-R 2-N (R 4R 5R 6) +-OOC-R 1(III) wherein, R 1, R 2Identical with the definition of front, R 3, R 4And R 5Represent hydrogen and alkyl, preferred especially all R with 1-2 atom 3, R 4And R 5Represent hydrogen.
The present invention also relates to following anti-hard caking agent: contain 0.2%-20% (weight), preferred 0.5%-5% (weight) as general formula (Ia) and salt (Ib), and oil or wax, and may contain weighting agent, various anti-hard caking agents, protective material or other additive.
As described, the present invention also relates to the preparation method of aforesaid partical with anti-hard caking agent, described method is characterised in that, as the compound R of (IV) formula 1-A 0(IV) with as (V) compd B of formula 0-R 2-B 0(V) reaction forms as (Ia) salt of formula: R 1-AB-R 2-BA-R 1(Ia) or as (VI) compound R of formula 1-B 0(VI) with as (VII) compd A of formula 0-R 2-A 0(VII) reaction forms as (Ib) the salt R of formula 1-BA-R 2-AB-R 1(Ib) wherein: (Ia), (Ib), (IV), (V), (VI) and (VII) A in the formula 0Represent anion-radicals, B 0Represent cation radical, R 1Represent monovalence hydrophobic organic radical, R 2Represent divalence hydrophobic organic radical, the A representative is corresponding to A 0The anion-radicals that forms, the B representative is corresponding to B 0The cation radical that forms.
So as preferred, B 0Be selected from base.Preferred at least one two B particularly 0Base is amino or its ammonium salt.
If B 0Base is added in R 2Form the diamines shown in (V) formula on the base, then diamines can be simple terminal diamines, and wherein two amino is added on the hydrocarbon framework or the polyamines of several amino is arranged on its chain.The amine that commercial value is arranged is inferior quadrol (EDA), diethylenetriamine (DETA), Triethylenetetramine (TETA) (TETA), tetren (TEPA), penten (PEHA), aminoethylpiperazine (AEP), piperazine (DEDA), and trimethylene diamine (1,2-PDA), 1, and the 3-diaminopropanes (1,3-PDA), imino-dipropylamine (IBPA), dimethylaminopropyl amine (DMAPA), menthyl diamines (MDA), triethylenediamine (TEDA), N, N, N ', N '-tetramethylene-diamine (TMEDA), N, N, N ', N '-tetramethylene-1,3-butanediamine (TMBDA) and hexa-methylene-1,3-butyl diamines (HMDA).
A typical amine is according to formula (VI), works as B 0Be added in R 1Form in the time of on the base, as methylamine, ethamine, just-propylamine, just-butylamine, just-amylamine or amylamine, just-hexylamine, just-octylame, just-and decyl amine, lauryl amine, tetradecy lamine, n-hexadecane amine, oily enamine and Stearyl Amine.
Aforementioned (IV) and (V) A in the formula 0The acidic groups of the acid of preferred self-contained organic substituent.Of this sort group be hydroxyl when the mineral acid of hydroxyl by alkyl such as alkyl, or-oxyl is as formation that alkoxyl group replaces.The most preferred acidic group that contains substituent acid is the carboxylic acid group who obtains from carbonic acid.Equally, can be used, under described situation, ion-exchange take place between the salt form anti-hard caking agent of the present invention by acidic group gained salt such as carboxylate salt.According to embodiment preferred, at least one is two A particularly 0Base is the carboxylic acid group in carboxylic acid group or the carboxylate salt.
A 0Can represent the residue of any carboxylic acid of following acid, and as preferred, carboxylic acid residues is by being added in R 1On the base to form monocarboxylic acid (shown in (IV) formula): butyric acid, caproic acid, sad, capric acid, lauric acid (laurostearic acid), tetradecanoic acid (TETRADECONIC ACID), Palmiticacid (palmitic acid), stearic acid (stearic acid), eicosanoic acid (20 sour) ， docosoics (behenic acid), wood cellulose acid (tetracosanoic acid), cerinic acid (hydroxyhexacosanoic acid) or the corresponding unsaturation acid (Δ-9,10-stearic acid) similar with oleic acid.
Work as A 0Description is added in R as (VII) formula 2Form di-carboxylic acid on the base, it can represent following any: oxalic acid, propanedioic acid, succsinic acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid, nonane dicarboxylic acid, decane dioctyl phthalate, undecane dioctyl phthalate and dodecane dioctyl phthalate.Preferred placement also is the succsinic acid by the by product acquisition of hexanodioic acid process, the mixture of hexanodioic acid and pentanedioic acid.
Before mention, to R in the product of the present invention 1And R 2Processing the time, acid and/or amine can contain heteroatoms in chain or as the substituting group in the chain.Depend on field and additive that anti-hard caking agent will use, chain also can be formed by siloxane unit and/or fluorocarbons.
In the method for the present invention to substituent R 1And R 2Explanation identical with explanation to product.
The special method of describing according to the present invention, (VIII) compound R of formula 1-A 0
R 1-COOH (VIII) or its response derivative, as acid anhydride, chloride of acid or salt are with the compd B of (IX) formula 0-R 2-B 0
H 2N-R 2-NH 2(IX) reaction, perhaps with its ammonium salt or other reactant salt, wherein, R 1And R 2Identical with former definition.
According to method of the present invention, if as (X) R of formula 1-B 0Compound, or its ammonium salt or other salt
R 1-NH 2(X) with (XI) compd A of formula 0-R 2-A 0
HOOC-R 2-COOH (XI) or response derivative (as acid anhydride, chloride of acid or its salt) react, also belong to favourable, R wherein 1And R 2As preceding definition.
When salt of the present invention derives from mol ratio R 1: R 2Be 2: 1 simple function group or bifunctional compound, then negatively charged ion and cationic components neutralize mutually.If depart from this equivalent proportioning (positively charged ion or negatively charged ion are excessive), found the performance of some fertilizer anti-hard caking agents better.According to embodiment of the present invention, aforesaid compound nonstoichiometry when reaction compares R 1: R 22: 11%-60%, preferred 1%-20%.
Negatively charged ion or positively charged ion can excessively make an addition in the product that makes in advance according to the present invention, or in the oil or wax that adopt in the Liniment mixture, or excessive making an addition in the Liniment mixture, the latter contains The compounds of this invention and oil or wax.According to embodiment of the present invention, by adding excessive identical anion surfactant (being contained in the salt of the present invention), or other suitablely selects anion surfactant, makes electric charge become negative.
As preferably,, the electric charge of anti-hard caking agent of the present invention is just being become by adding excessive cats product (can be identical or different) with the component of used salt of the present invention.
The inventive method is implemented by physical method, for example, with mix and possible heating under, in difference oil in batches, add each reactant, perhaps reactant is mixed with the oil of same batch also and might heat.Generally, about two mole compound R 1-A 0Or R 1-B 0In oil, mix as coating, and about one mole compd B 0-R 2-B 0Or corresponding A 0-R 2-A 0Be mixed in respectively in the mixture as coating.Mixture mixes, and then heats as needs.Other method is to adopt compound R 1-A 0And B 0-R 2-B 0(or R 1-B 0And A 0-R 2-A 0) be mixed in in the oil in batches and heat spontaneous formation salt in the mixture.For example, the salt of uncle or secondary diamine and carboxylic acid, or the salt of dicarboxylic acid and uncle or secondary amine all can prepare in this way.
According to second embodiment of the present invention, reactant or add respectively in the different solvents in batches, and then mix, perhaps add with in the solvent in batches, form salt behind the evaporating solvent.So, two moles compound R 1-A 0Or R 1-B 0With about one mole compd B 0-R 2-B 0Or corresponding A 0-R 2-A 0Be dissolved in respectively in the same organic solvent, again each solvent added together, or compound dissolution also mixes in a collection of solvent.The salt of aforesaid compound obtains after evaporating solvent.
According to the 3rd embodiment of the present invention, be preferably the reactant of acid salt and ammonium salt, perhaps add separately in the different water in batches, stir the back and merge, or add with after in the water in batches, from water, isolate precipitated product.Generally, about two moles compound R 1-A 0Or R 1-B 0Compd B with one mole 0-R 2-B 0Or A 0-R 2-A 0Corresponding dissolving together, or as preferred, be dissolved in the water respectively.The salt that forms almost completely is separated in the nonaqueous phase, and it evaporates then from wherein being told (can heat if desired) by machinery and/or for example using organic solvent extraction.Work as compound R 1-A 0(R 1-B 0) or B 0-R 2-B 0(A 0-R 2-A 0) both one of be salt, or the two is when all being salt, when for example salt is quaternary ammonium halide and alkali metal carboxylate, the suitable preparation of this method salt of the present invention.Corresponding ion such as halogen and basic metal will be retained in the aqueous solution.
The fact that above-mentioned equilibrium ratio certain and in certain limitation improves the anti-anti-caking of product interrelates.
According to another embodiment of the present invention, reactant is added in the overlay of partical particle and reacts in the hot environment of particle overlay.Generally, the precursor negatively charged ion of salt of the present invention and positive particle join butyrous in the preparation process of Liniment respectively or melt in the wax material of body shape.Therefore if the residing temperature of mixture that obtains surpasses the melting point of salt of the present invention, then at Liniment before handled partical surface cool, the anti-caking of the present invention salt can not form.
The present invention also relates to salt as general formula (Ia)
R 1-AB-R 2-BA-R 1(Ia) or as the salt of general formula (Ib)
R 1-BA-R 2-AB-R 1(Ib) wherein, R 1Represent monovalence hydrophobic organic radical independently, R 2Represent divalence hydrophobic organic radical, on behalf of negatively charged ion and B, A represent positively charged ion independently independently, also relates to described salt as the anti-hard caking agent of partical or as the purposes of the component of described reagent.
The explanation of aforementioned corresponding product of the present invention and method also is suitable for and the relevant explanation of described reagent purposes.
When reality enforcement was of the present invention, aforesaid salt wax coating uniformly was coated on the warm partical, and under described situation, anti-caking block protection film forms at particle surface.
According to another embodiment, aforesaid salt is the component of the mixture of oil or wax, so prevent the anti-caking of partical in unprecedented mode.
A kind of preferred common method is, adopts the mix reagent that is dispersed in oil or the wax Liniment mixture and makes it be coated on the partical surface by spraying drop in small, broken bits.The salt temperature that contains oil or wax Liniment is preferably very high, so that salt of the present invention is dissolved or dispersed in the used oil basically, the latter adjusts the viscosity of mixture to abundant low level, so guarantees the sprinkling of mixture.In addition, oil, wax are in melting state and also suit.
The present invention also relates to partical, it is characterized in that, particle is through anti-hard caking agent or contain the mixture process of described anti-hard caking agent, and wherein, described anti-hard caking agent is the salt R as shown in the formula (Ia) 1-AB-R 2-BA-R 1(Ia) or as the salt R of general formula (Ib) 1-BA-R 2-AB-R 1(Ib) wherein, R 1Represent monovalence hydrophobic organic radical independently, R 2Represent divalence hydrophobic organic radical, on behalf of negatively charged ion and B, A represent positively charged ion independently independently.
Aforementioned corresponding anti-hard caking agent of the present invention with and its production and use explanation also be applicable to partical.
The salt that is used for the partical anti-hard caking agent is preferably as general formula (II) R 1-N (R 3R 4R 5) +-OOC-R 2-COO- +N (R 4R 5R 6)-R 1(II) wherein, R 1And R 2The same, R 3, R 4And R 5Represent hydrogen and the alkyl with 1 to 2 carbon atom, particularly all R 3, R 4And R 5Represent hydrogen.As an alternative, salt is preferably as general formula (III) R 1-COO- +N (R 3R 4R 5)-R 2-N (R 4R 5R 6) +-OOC-R 1(III) wherein, R 1And R 2The same, R 3, R 4And R 5Represent hydrogen and the alkyl with 1 to 2 carbon atom, particularly all R 3, R 4And R 5Represent hydrogen.
Partical of the present invention can only apply with aforementioned anti-hard caking agent, or with the mixture coating, the latter is also contained oil or wax in addition except that containing aforesaid salt, and may contain weighting material and other anti-hard caking agent, protective material and additive.
Partical of the present invention can be for example powder, powder, dust, scale, slag, seed, particle and partical.Product also can be inorganic salt, inorganic salt mixt or contain the partical of aforementioned product.Particularly, partical can be the N-P-K fertilizer of fertilizer as easily luming usually.Anti-hard caking agent of the present invention is very suitable to such fertilizer.
Embodiment
The present invention is further described to adopt these embodiment. Embodiment 1
Making mol ratio by technical grade uncle Stearyl Amine (Noram S/CECA) and hexanodioic acid is 2: 1 salt (according to salt of the present invention).Hexanodioic acid consumption 2.9 grams during the preparation sample.Methyl alcohol is the solvent of hexanodioic acid, and ether is the solvent of amine. Embodiment 2 (comparative example)
Program according to embodiment 1 makes salt, but used non-be technical grade uncle Stearyl Amine, but the technical grade of corresponding amount uncle stearic acid diamines R-NH-CH 2-CH 2-CH 2-NH 2(InipolDS/CECA). Embodiment 3
Get 1 part of weight, the dibasic amino acid salt that in embodiment 1-2, prepares and the paraffin mineral oil of 9 parts of weight, in 80 ℃ of mixing of temperature.Spray 80 ℃ of Liniment mixtures with 2 gram/kilograms or 4 gram/kilogram consumptions to 40 ℃ of warm fertilizer surfaces, spray talcum powder (Finntalk P40) in the surface with 4 gram/kilogram consumptions then, so prevent fertilizer agglomeration, detect the performance of made Liniment mixture.Coated fertilizer is at 25 ℃, and relative humidity is incubated 2 hours 75% time.Five parts of fertilizer, each heavy 100 the gram, be positioned in the plastics bag, then with sack at 1kg/cm 2Pressure was transferred one day, and after this sack is one by one from 50 centimetres of high falling.Fertilizer sieved with 7.1 millimeters sieve then.Measure caking tendency with the amount of staying the fertilizer particle on the sieve.Obtain following result:
Salt (according to the present invention) 2% coating 1.5 464% coatings 1.5 42 of salt (Comparative Examples) 2% coating 1.1 44% coatings 1.2 0 embodiment 2 of 1.4 47 embodiment 1 of moisture content % sheet content % uncoated Embodiment 4
Mixing by the salt of hexanodioic acid and the preparation of technical grade list stearylamide of paraffin mineral oil and 4% (weight) according to embodiment 1.The program of mixture employing embodiment 3 detects the inhibition caking tendency of fertilizer 20-0-15 (N-P-K).
The commercial Liniment mixture that is easy to get is elected to be the contrast medium to this fertilizer.Obtain following result:
The salt of the present invention of 1.4 47 embodiment 1 of moisture content % sheet content % uncoated, content 4%2% coating, 1.2 134% coatings, 1.2 6 commercial Liniment mixtures (for contrast) 2% coating 1.4 284% coatings 1.3 23 in the oil Embodiment 5
With theoretical molar than 1: 2 and adjust negatively charged ion or cationic components excessive, the salt of paraffin mineral oil and 4% (weight) hexanodioic acid and technical grade list stearylamide is mixed, make and be coated with application oil.The caking tendency of NPK fertilizer 20-4-8 (N-P-K) is measured with the method that embodiment 3 describes, and at that time, fertilizer per ton adopts 2 kilograms to be coated with unction and 2.5 kilograms of talcum powder (caking I), and 4 kilograms are coated with unction and 4 kilograms of talcum powder (caking II).Liniment caking %
I II theoretical molar is than the excessive 8.2 moles of % 33 of excessive 4.1 moles of % 11 5 stearylamides of excessive 19.7 moles of % 83 stearylamides of excessive 9.9 moles of % 97 stearylamides of 19 7 stearylamides Embodiment 6
Be coated with negatively charged ion or cationic in the application oil (containing 1: 2 salt of mol ratio between hexanodioic acid and technical grade list stearylamide) by increase, promptly add excessive octylame or sad, proceed the detection among the embodiment 5.Liniment caking %
Excessive 50 moles of %, 42 sad excessive 22 moles of %, the 33 sad excessive 44 moles of % 62 of excessive 25 moles of % 74 octylames of I II octylame Embodiment 7
Adopt fertilizer NPK20-0-15, and the salt between hexanodioic acid and the stearylamide (even employing theoretical molar effect this moment is also excellent), the detection of embodiment 5-6 repeated.Positively charged ion or the anionic property and further reduce of the tendency that specimen forms sheet by increasing Liniment: Liniment caking %
I II theoretical molar is than excessive 50 % by mole 40 sad excessive 22 % by mole 39 sad excessive 44 % by mole 21 6 of excessive 25 % by mole of 21 octylame of excessive 8.2 % by mole of 51 octylame of excessive 4.1 % by mole of 71 adipic acid of excessive 19.7 % by mole of 55 adipic acid of excessive 9.9 % by mole of 61 stearmide of 93 stearmidesEmbodiment 8 (preparing in the oil)
Preparation 50 gram fertilizer are coated with unction, include the oil that contains paraffin of 96% (weight), and the compound that derives from stearic acid and ethylene diamine of 4% (weight), and at that time, 1.79 gram stearic acid are dissolved in the warm oil and melt therein; Under 80 ℃ of temperature, add 0.21 gram ethylene diamine gradually; Limpid solution becomes muddiness, but the viscosity under 70-80 ℃ is still low, treats to spray through nozzle. Embodiment 9(amine is excessive)
Preparation fertilizer is coated with unction, include the oil of 97% (weight), the compound that is formed by stearic acid and ethylene diamine of 2% (weight), and 1% technical grade stearylamide, the unction that is coated with of so a embodiment 8 contains the technical grade stearylamide that is dissolved in the same quality base oil and mixes with a.Sample retention is at temperature 70-80 ℃, and viscosity still is suitable for spraying through nozzle. Embodiment 10(comparing embodiment)
According to KirkOthmer, second, the 252nd page, the third edition (1978), 1 mole of ethylene diamine is mixed with two moles of stearic acid gradually, and under nitrogen environment, be heated to 165-175 ℃, and continue heating down at 180-185 ℃ and no longer change up to product (weight), make ethylene bis stearamide R-CO-NH-CH 2-CH 2-NH-CO-R, wherein R derives from stearic alkyl.After the product cooling is class wax.The hot differential scanning of amount of samples (DCS) is analyzed, and at that time, about 2 milligrams sample heats with 4 ℃/minute speed.The thawing of corresponding diamines endotherm(ic)peak occurs at 142 ℃. Embodiment 11(comparing embodiment)
Corresponding embodiment 10 makes Liniment.In the preparation, do not adopt stearic acid and ethylene diamine, but adopt and the corresponding mole dosage of embodiment 10 made diamide.Diamide mixes by a diverting device with the oil that is heated to 80 ℃, but it does not dissolve.In the gained mixture then at 80 ℃ of mixtures that add down oil and stearylamide, and in the blended process elevated temperature, dissolve down at 126 ℃ up to diamide.Under described temperature, mixture is thickness still, but after cooling, it forms deleterious curing.Mixture contains the oil of 97.1% (weight), the technical grade stearylamide of the ethylene bis stearamide of 1.9% (weight) and 1% (weight). Embodiment 12(mummification compound)
According to following mode, make a kind of mixture, can dry state carry and can be used as anti-caking product component (making it in warm oil, mix) with other possible component, be prepared as follows:
10.7 the gram ethylene diamine is sneaked in the stiff resin acid powder of 89.3 grams, so temperature is brought up to 49 ℃.Mixture cooling back gained caking decomposes, and dry, in small, broken bits and tractable product like this, the dsc analysis of product show, big endotherm(ic)peak is arranged about 96 ℃, and corresponding stearic melting point has little endotherm(ic)peak (55 ℃).Utilize the thermogravimetric device to confirm, during heating, (weight) of sample begins to descend when being higher than about 100 ℃, begins to change mild but changes more than 160 ℃ the time more precipitously approximately, and this shows that sample contains carboxyl and amino, discharges water outlet in the reaction.
According to the present invention, the solid mechanical mixture of other solid chemical compound is as hexanodioic acid and the suitable too anti-hard caking agent that is used as of stearylamide.According to the present invention, under described situation, only compound just begins to take shape when mixture is dissolved in the warm oil. Embodiment 13 (oil concentrate)
44.6 the gram stearic acid under about 55 ℃, melts in 50 gram oil.53.6 gram technical grade ethylene diamine adds in the mixture.Obtain the yellow suspension thing after the cooling, its dsc analysis is presented at 93 ℃ endotherm(ic)peak.Utilize the thermogravimetric device to confirm, sample (weight) begins to descend when being heated above about 100 ℃, begins to change mild but changes more than 160 ℃ the time more precipitous.

Claims (40)

1. the anti-hard caking agent that is used for partical is characterized in that it is a salt as general formula (Ia):
R 1-AB-R 2-BA-R 1(Ia) or as general formula (Ib):
R 1-BA-R 2-AB-R 1 (Ib)
Wherein, R 1Represent monovalence hydrophobic organic radical independently, R 2Represent divalence hydrophobic organic radical, on behalf of negatively charged ion and B, A represent positively charged ion independently independently.
2. according to the anti-hard caking agent of claim 1, it is characterized in that cation radical B represents ammonium ion.
3. according to the anti-hard caking agent of claim 1 or 2, it is characterized in that the anion-radicals that anion-radicals A representative is made by organic residue replacing acid.
4. according to the anti-hard caking agent of claim 3, it is characterized in that anion-radicals A represents carboxylic acid ion.
5. according to the anti-hard caking agent of claim 1 or 4, it is characterized in that R 1It is alkyl with at least 7 carbon atoms.
6. according to the anti-hard caking agent of claim 5, it is characterized in that R 1It is alkyl with 10-22 carbon atom.
7. according to the anti-hard caking agent of claim 1 or 6, it is characterized in that R 2Representative has the alkylene of 1-22 carbon atom.
8. according to the anti-hard caking agent of claim 7, it is characterized in that R 2Representative has the alkylene of 2-8 carbon atom.
9. according to the anti-hard caking agent of claim 1 or 8, it is characterized in that it is a salt as general formula (II):
R 1-N(R 3R 4R 5) +-OOC-R 2-COO- +N(R 4R 5R 6)-R 1 (II)
Wherein, R 1And R 2The same, R 3, R 4And R 5Represent hydrogen and alkyl with 1 to 2 carbon atom.
10. anti-hard caking agent according to Claim 8 is characterized in that all R 3, R 4And R 5All represent hydrogen.
11., it is characterized in that it is a salt as general formula (III) according to the anti-hard caking agent of claim 1 or 8:
R 1-COO- +N(R 3R 4R 5)-R 2-N(R 4R 5R 6) +-OOC-R 1 (III)
Wherein, R 1And R 2The same, R 3, R 4And R 5Represent hydrogen and alkyl with 1 to 2 carbon atom.
12., it is characterized in that all R according to the anti-hard caking agent of claim 11 3, R 4And R 5Represent hydrogen.
13. anti-hard caking agent is characterized in that it contains the general formula of 0.2%-20% (weight) (Ia) or salt (Ib) and oil or wax, and may contain weighting material and other anti-hard caking agent, protective material and additive.
14., it is characterized in that comprising 0.5%-5% (weight) general formula (Ia) or salt (Ib) according to the anti-hard caking agent of claim 13.
15. the anti-hard caking agent according to claim 1 is characterized in that, for adjusting salt R 1-AB-R 2-BA-R 1Or R 1-BA-R 2-AB-R 1The purpose of electric charge, it still contains the excessive cation surface activating compound of 5%-100 mole %.
16. the partical of aforementioned arbitrary claim is characterized in that the compound suc as formula (IV) with the preparation method of anti-hard caking agent
R 1-A 0 (IV)
With as (V) compound of formula
B 0-R 2-B 0 (V)
Reaction forms as (Ia) salt of formula
R 1-AB-R 2-BA-R 1 (Ia)
Perhaps, as the compound of (VI) formula
R 1-B 0 (VI)
With as (VII) compound of formula
A 0-R 2-A 0 (VII)
Reaction forms as (Ib) salt of formula
R 1-BA-R 2-AB-R 1 (Ib)
Wherein, (Ia), (Ib), (IV), (V), (VI) and (VII) A in the formula 0Represent anion-radicals, B 0Represent cation radical, R 1Represent monovalence hydrophobic organic radical, R 2Represent divalence hydrophobic organic radical, the A representative is corresponding to A 0The negatively charged ion that forms, the B representative is corresponding to B 0The positively charged ion that forms.
17. the method according to claim 16 is characterized in that B 0Represent amino or its ammonium salt.
18. the method according to claim 16 or 17 is characterized in that A 0Be selected from the anionic group that contains organic substituent acid.
19., it is characterized in that two A according to the method for claim 18 0Base is carboxylic acid or its salt.
20. the method according to claim 17 or 19 is characterized in that R 1It is the alkyl that has 7 carbon atoms at least.
21. the method according to claim 20 is characterized in that R 1It is alkyl with 10-22 carbon atom.
22. the method according to claim 16 or 21 is characterized in that R 2It is alkylene with 1-22 carbon atom.
23. the method according to claim 22 is characterized in that R 2It is alkylene with 2-8 carbon atom.
24. the method according to claim 16 is characterized in that compound R 1-A 0Have formula (VIII):
R 1-COOH (VIII)
Or its active salt and compd B 0-R 2-B 0, have (IX) formula:
H 2N-R 2-NH 2 (IX)
Or its ammonium salt reaction, wherein, R 1And R 2Define the same.
25., it is characterized in that the compound R of formula (X) according to the method for claim 16 1-B 0
R 1-NH 2 (X)
Or its ammonium salt and (XI) compd A of formula 0-R 2-A 0
HOOC-R 2-COOH (XI)
Or its active salt reaction, wherein R 1And R 2As preceding definition.
26., it is characterized in that the R of the compound of question response according to the method for claim 24 or 25 1: R 22: 1 any direction of the relative stoichiometric ratio of mol ratio departs from 1%-20%.
27. according to the method for claim 16, it is characterized in that reactant acid and amine with mix and possible heating under add separately in the different oil in batches, or reactant is added in the oil of batch together and may heats then.
28., it is characterized in that reactant or add separately in the different solvents in batches according to the method for claim 27, then it is merged, perhaps join in the solvent of same batch and after evaporating solvent, form salt.
29., it is characterized in that as the reactant of acid salt and ammonium salt or add separately in the different water in batches according to the method for claim 27, then it is merged, perhaps join in the water of same batch and follow precipitation separation product from water.
30., it is characterized in that reactant is added in the coating of partical particle and reacts in the high temperature coated environment of particle according to the method for claim 27.
31. as the anti-hard caking agent of partical or as the purposes as the salt of general formula (Ia) of described reagent component
R 1-AB-R 2-BA-R 1 (Ia)
Or as the purposes of the salt of general formula (Ib)
R 1-BA-R 2-AB-R 1 (Ib)
Wherein, R 1Represent monovalence hydrophobic organic radical independently, R 2Represent divalence hydrophobic organic radical, on behalf of negatively charged ion and B, A represent independent positively charged ion independently.
32. the purposes of claim 31 makes oil or wax Liniment mixture heating up to generate liquid low viscosity mixtures thus, latter's rapidly dissolvable also disperses aforementioned salt, and can be dispersed in the particle surface of partical by spraying with fine drop subsequently.
33. partical is characterized in that the product particle handles with anti-hard caking agent, anti-hard caking agent is the salt as shown in the formula (Ia)
R 1-AB-R 2-BA-R 1 (Ia)
Or as the salt of general formula (Ib)
R 1-BA-R 2-AB-R 1 (Ib)
Wherein, R 1Represent monovalence hydrophobic organic radical independently, R 2Represent divalence hydrophobic organic radical, on behalf of negatively charged ion and B, A represent independent positively charged ion independently.
34., it is characterized in that salt such as general formula (II) according to the partical of claim 33
R 1-N(R 3R 4R 5) +-OOC-R 2-COO- +N(R 4R 5R 6)-R 1 (II)
Wherein, R 1And R 2The same, R 3, R 4And R 5Represent hydrogen or have the alkyl of 1 to 2 carbon atom.
35., it is characterized in that particularly all R according to the partical of claim 33 3, R 4And R 5Represent hydrogen.
36., it is characterized in that salt such as general formula (III) according to the partical of claim 33 or 34
R 1-COO- +N(R 3R 4R 5)-R 2-N(R 4R 5R 6) +-OOC-R 1 (III)
Wherein, R 1And R 2The same, R 3, R 4And R 5Represent hydrogen or have the alkyl of 1 to 2 carbon atom.
37., it is characterized in that all R according to the partical of claim 36 3, R 4And R 5Represent hydrogen.
38. according to the partical of claim 33, it is characterized in that particle surface handles through mixture, mixture except that saliferous, still oil-containing or wax, and may contain weighting material and other anti-hard caking agent, protective material and additive.
39., it is characterized in that it is a fertilizer according to the partical of claim 33.
40., it is characterized in that it is a N-P-K fertilizer according to the partical of claim 39.
CN96198625A 1995-10-30 1996-10-29 An anti-caking agent Expired - Fee Related CN1102134C (en)

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ES2319367B1 (en) 2007-07-03 2010-01-12 Kao Corporation, S.A. ANTIAPELMAZANTES COMPOSITIONS FOR FERTILIZERS.
CN102300835B (en) 2009-01-29 2016-09-14 国际壳牌研究有限公司 Sulfur-containing fertilizer and preparation method thereof
CN102300834A (en) 2009-01-29 2011-12-28 国际壳牌研究有限公司 Sulphur-containing fertilizers and process for the preparation thereof
CN102243182B (en) * 2011-04-08 2012-11-28 湖北富邦科技股份有限公司 Detection method for phosphate ester content in powdery anti-caking agent
WO2013098404A1 (en) 2011-12-29 2013-07-04 Shell Internationale Research Maatschappij B.V. Processes for the manufacture of sulphur-containing compositions and sulphur-containing fertilizer compositions
CN104291917A (en) * 2013-07-16 2015-01-21 中国地质大学（北京） Bentonite-based granular composite fertilizer anti-caking agent and preparation method thereof
CN103663498B (en) * 2013-09-24 2016-01-20 北京艾思合众环保科技有限公司 A kind of method preventing Sodium Thiocyanate 99 from luming
KR102185742B1 (en) * 2017-11-22 2020-12-02 주식회사 엘지화학 Method for preparing graft copolymer powder
CN109180351B (en) * 2018-11-06 2021-10-29 广东省生物工程研究所（广州甘蔗糖业研究所） Moisture-proof silicon-magnesium-boron-zinc composite granular fertilizer and preparation method thereof

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US3926841A (en) * 1972-06-05 1975-12-16 Lever Brothers Ltd Anti-caking composition

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FR2460706A1 (en) * 1979-07-13 1981-01-30 Produits Ind Cie Fse ANTIMOTTANT PRODUCTS AND TREATMENTS BASED ON AMINE SALTS

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US3926841A (en) * 1972-06-05 1975-12-16 Lever Brothers Ltd Anti-caking composition

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WO1997016396A1 (en) 1997-05-09

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